997 resultados para Homogeneous Media


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The investigation into the encapsulation of gold nanoparticles (AuNPs) by poly(methyl methacrylate) (PMMA) was undertaken. This was performed by three polymerisation techniques including: grafting PMMA synthesised by reversible addition-fragmentation chain transfer (RAFT) polymerisation to AuNPs, grafting PMMA synthesised by atom transfer radical polymerisation (ATRP) from the surface of functionalised AuNPs and by encapsulation of AuNPs within PMMA latexes produced through photo-initiated oil-in-water (o/w) miniemulsion polymerisation. The grafting of RAFT PMMA to AuNPs was performed by the addition of the RAFT functionalised PMMA to citrate stabilised AuNPs. This was conducted with a range of PMMA of varying molecular weight distribution (MWD) as either the dithioester or thiol end-group functionalities. The RAFT PMMA polymers were characterised by gel permeation chromatography (GPC), ultraviolet-visible (UV-vis), Fourier transform infrared-attenuated total reflectance (FTIR-ATR), Fourier transform Raman (FT-Raman) and proton nuclear magnetic resonance (1H NMR) spectroscopies. The attachment of PMMA to AuNPs showed a tendency for AuNPs to associate with the PMMA structures formed, though significant aggregation occurred. Interestingly, thiol functionalised end-group PMMA showed very little aggregation of AuNPs. The spherical polymer-AuNP structures did not vary in size with variations in PMMA MWD. The PMMA-AuNP structures were characterised using scanning electron microscopy (SEM), transition electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and UV-vis spectroscopy. The surface confined ATRP grafting of PMMA from initiator functionalised AuNPs was polymerised in both homogeneous and heterogeneous media. 11,11’- dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane] (DSBr) was used as the surface-confined initiator and was synthesised in a three step procedure from mercaptoundecanol (MUD). All compounds were characterised by 1H NMR, FTIR-ATR and Raman spectroscopies. The grafting in homogeneous media resulted in amorphous PMMA with significant AuNP aggregation. Individually grafted AuNPs were difficult to separate and characterise, though SEM, TEM, EDAX and UV-vis spectroscopy was used. The heterogeneous polymerisation did not produce grafted AuNPs as characterised by SEM and EDAX. The encapsulation of AuNPs within PMMA latexes through the process of photoinitiated miniemulsion polymerisation was successfully achieved. Initially, photoinitiated miniemulsion polymerisation was conducted as a viable low temperature method of miniemulsion initiation. This proved successful producing a stable PMMA with good conversion efficiency and narrow particle size distribution (PSD). This is the first report of such a system. The photo-initiated technique was further optimised and AuNPs were included into the miniemulsion. AuNP encapsulation was very effective, producing reproducible AuNP encapsulated PMMA latexes. Again, this is the first reported case of this. The latexes were characterised by TEM, SEM, GPC, gravimetric analysis and dynamic light scattering (DLS).

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Homogenization of partial differential equations is relatively a new area and has tremendous applications in various branches of engineering sciences like: material science,porous media, study of vibrations of thin structures, composite materials to name a few. Though the material scientists and others had reasonable idea about the homogenization process, it was lacking a good mathematical theory till early seventies. The first proper mathematical procedure was developed in the seventies and later in the last 30 years or so it has flourished in various ways both application wise and mathematically. This is not a full survey article and on the other hand we will not be concentrating on a specialized problem. Indeed, we do indicate certain specialized problems of our interest without much details and that is not the main theme of the article. I plan to give an introductory presentation with the aim of catering to a wider audience. We go through few examples to understand homogenization procedure in a general perspective together with applications. We also present various mathematical techniques available and if possible some details about some of the techniques. A possible definition of homogenization would be that it is a process of understanding a heterogeneous (in-homogeneous) media, where the heterogeneties are at the microscopic level, like in composite materials, by a homogeneous media. In other words, one would like to obtain a homogeneous description of a highly oscillating in-homogeneous media. We also present other generalizations to non linear problems, porous media and so on. Finally, we will like to see a closely related issue of optimal bounds which itself is an independent area of research.

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Dynamic rupture simulations are unique in their contributions to the study of earthquake physics. The current rapid development of dynamic rupture simulations poses several new questions: Do the simulations reflect the real world? Do the simulations have predictive power? Which one should we believe when the simulations disagree? This thesis illustrates how integration with observations can help address these questions and reduce the effects of non-uniqueness of both dynamic rupture simulations and kinematic inversion problems. Dynamic rupture simulations with observational constraints can effectively identify non-physical features inferred from observations. Moreover, the integrative technique can also provide more physical insights into the mechanisms of earthquakes. This thesis demonstrates two examples of such kinds of integration: dynamic rupture simulations of the Mw 9.0 2011 Tohoku-Oki earthquake and of earthquake ruptures in damaged fault zones:

(1) We develop simulations of the Tohoku-Oki earthquake based on a variety of observations and minimum assumptions of model parameters. The simulations provide realistic estimations of stress drop and fracture energy of the region and explain the physical mechanisms of high-frequency radiation in the deep region. We also find that the overridding subduction wedge contributes significantly to the up-dip rupture propagation and large final slip in the shallow region. Such findings are also applicable to other megathrust earthquakes.

(2) Damaged fault zones are usually found around natural faults, but their effects on earthquake ruptures have been largely unknown. We simulate earthquake ruptures in damaged fault zones with material properties constrained by seismic and geological observations. We show that reflected waves in fault zones are effective at generating pulse-like ruptures and head waves tend to accelerate and decelerate rupture speeds. These mechanisms are robust in natural fault zones with large attenuation and off-fault plasticity. Moreover, earthquakes in damaged fault zones can propagate at super-Rayleigh speeds that are unstable in homogeneous media. Supershear transitions in fault zones do not require large fault stresses. In the end, we present observations in the Big Bear region, where variability of rupture speeds of small earthquakes correlates with the laterally variable materials in a damaged fault zone.

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Within the framework of classic electromagnetic theories, we have studied the sign of refractive index of optical medias with the emphases on the roles of the electric and magnetic losses and gains. Starting from the Maxwell equations for an isotropic and homogeneous media, we have derived the general form of the complex refractive index and its relation with the complex electric permittivity and magnetic permeability, i.e. n = root epsilon mu, in which the intrinsic electric and magnetic losses and gains are included as the imaginary parts of the complex permittivity and permeability, respectively, as epsilon = epsilon(r) + i(epsilon i) and mu = mu(r) + i mu(i). The electric and magnetic losses are present in all passive materials, which correspond, respectively, to the positive imaginary permittivity and permeability epsilon(i) > 0 and mu(i) > 0. The electric and magnetic gains are present in materials where external pumping sources enable the light to be amplified instead of attenuated, which correspond, respectively, to the negative imaginary permittivity and permeability epsilon(i) < 0 and mu(i) < 0. We have analyzed and determined uniquely the sign of the refractive index, for all possible combinations of the four parameters epsilon(r), mu(r), epsilon(i), and mu(i), in light of the relativistic causality. A causal solution requires that the wave impedance be positive Re {Z} > 0. We illustrate the results for all cases in tables of the sign of refractive index. One of the most important messages from the sign tables is that, apart from the well-known case where simultaneously epsilon < 0 and mu < 0, there are other possibilities for the refractive index to be negative n < 0, for example, for epsilon(r) < 0, mu(r) > 0, epsilon(i) > 0, and mu(i) > 0, the refractive index is negative n < 0 provided mu(i)/epsilon(i) > mu(r)/vertical bar epsilon(r)vertical bar. (c) 2006 Elsevier B.V. All rights reserved.

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A transesterificação metílica em meio homogêneo é catalisada por bases, tais como hidróxidos e alcóxidos de sódio ou potássio e se processa em baixa temperatura de reação, mesmo em escala industrial. A utilização de catalisadores formados por sólidos básicos aparece como uma alternativa promissora aos processos homogêneos convencionais, tendo em vista as inúmeras vantagens como a redução da ocorrência das reações indesejáveis de saponificação e redução de custos dos processos pela diminuição do número de operações associadas. Em estudos anteriores realizados pelo grupo, catalisadores a base de Mg/La com diferentes composições químicas (9:1, 1:1 e 1:9) mostraram-se promissores para a obtenção de ésteres metílicos via reação de transesterificação, porém não foi possível fazer uma correlação entre atividade catalítica e as propriedades físico-químicas quando toda a série foi considerada. Assim, a realização de um estudo de caráter fundamental, baseado em reações modelo e uso de moléculas sonda, permite avançar no entendimento das propriedades de superfície destes catalisadores. Portanto, o presente trabalho estuda a reação entre metanol e acetato de etila em catalisadores a base de Mg/La utilizando espectroscopia de reflectância difusa no infravermelho com transformada de Fourier (DRIFTS) acoplada a espectrometria de massas (MS) identificando os intermediários e produtos formados para determinar a rota reacional. As análises de difração de raios X mostram que os precursores são predominantemente compostos por carbonatos hidratados de magnésio (Mg/La 1:1 e 9:1) e de lantânio (Mg/La 1:9). Os perfis de decomposição térmica e difratogramas de raios X obtidos a partir de tratamento térmico in situ indicaram que estes carbonatos se decompõem apenas a partir de 750 C. As análises de Dessorção a Temperatura Programada realizadas com moléculas sonda, metanol e acetato de etila, mostraram a adsorção em maior quantidade do metanol independente da composição química do sólido. A partir dos resultados obtidos por DRIFTS-MS foi proposta uma rota reacional para a reação de transesterificação do acetato de etila e metanol, que ocorre via adsorção do metanol e do acetato de etila na superfície do catalisador, seguida da formação de um intermediário tetraédrico formado pelas moléculas adsorvidas, que sofre um rearranjo formando etanol, acetato de metila, acetona e metano. Simultaneamente, parte do metanol adsorvido como metoxi monodentado é desidrogenado formando formiatos que são dessorvidos na forma de formaldeído e decompostos formando CO2 e H2

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In an earlier study on intersonic crack propagation, Gao et al. (J. Mech. Phys. Solids 49: 2113-2132, 2001) described molecular dynamics simulations and continuum analysis of the dynamic behaviors of a mode II dominated crack moving along a weak plane under a constant loading rate. The crack was observed to initiate its motion at a critical time after the onset of loading, at which it is rapidly accelerated to the Rayleigh wave speed and propagates at this speed for a finite time interval until an intersonic daughter crack is nucleated at a peak stress at a finite distance ahead of the original crack tip. The present article aims to analyze this behavior for a mode III crack moving along a bi-material interface subject to a constant loading rate. We begin with a crack in an initially stress-free bi-material subject to a steadily increasing stress. The crack initiates its motion at a critical time governed by the Griffith criterion. After crack initiation, two scenarios of crack propagation are investigated: the first one is that the crack moves at a constant subsonic velocity; the second one is that the crack moves at the lower shear wave speed of the two materials. In the first scenario, the shear stress ahead of the crack tip is singular with exponent -1/2, as expected; in the second scenario, the stress singularity vanishes but a peak stress is found to emerge at a distance ahead of the moving crack tip. In the latter case, a daughter crack supersonic with respect to the softer medium can be expected to emerge ahead of the initial crack once the peak stress reaches the cohesive strength of the interface.

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By seismic tomography, interesting results have been achieved not only in the research of the geosphere with a large scale but also in the exploration of resources and projects with a small scale since 80'. Compared with traditional inversion methods, seismic tomography can offer more and detailed information about subsurface and has been being paid attention by more and more geophysicists. Since inversion based on forward modeling, we have studied and improved the methods to calculate seismic traveltimes and raypaths in isotropic and anisotropic media, and applied the improved forward methods to traveltime tomography. There are three main kinds of methods to calculate seismic traveltime field and its ray path distribution, which are ray-tracing theory, eikonal equation by the finite-difference and minimum traveltime tree algorithm. In ray tracing, five methods are introduced in the paper, including analytic ray tracing, ray shooting, ray bending, grid ray tracing and rectangle grid ray perturbation with three points. Finite-difference solution of eikonal equation is very efficient in calculation of seismic first-break, but is awkward in calculation of reflection traveltimes. We have put forward a idea to calculate traveltimes of reflected waves using a combining way of eikonal equation method and other one in order to improve its capability of dealing with reflection waves. The minimum traveltime tree algorithm has been studied with emphases. Three improved algorithms are put forward on the basis of basic algorithm of the minimum traveltime tree. The first improved algorithm is called raypath tracing backward minimum traveltime algorithm, in which not only wavelets from the current source but also wavelets from upper source points are all calculated. The algorithm can obviously improve the speed of calculating traveltimes and raypaths in layered or blocked homogeneous media and keep good accuracy. The second improved algorithm is raypath key point minimum traveltime algorithm in which traveltimes and raypaths are calculated with a view of key points of raypaths (key points of raypths mean the pivotal points which determine raypaths). The raypath key point method is developed on the basis of the first improved algorithm, and has better applicability. For example, it is very efficient even for inhomogeneous media. Another improved algorithm, double grid minimum traveltime tree algorithm, bases upon raypath key point scheme, in which a model is divided with two kinds of grids so that the unnecessary calculation can be left out. Violent undulation of curved interface often results in the phenomenon that there are no reflection points on some parts of interfaces where there should be. One efficacious scheme that curved interfaces are divided into segments, and these segments are treated respectively is presented to solve the problem. In addition, the approximation to interfaces with discrete grids leads to large errors in calculation of traveltimes and raypaths. Noting the point, we have thought a new method to remove the negative effect of mesh and to improve calculation accuracy by correcting the traveltimes with a little of additional calculation, and obtained better results.

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Tese dout., Engenharia electrónica e computação - Processamento de sinal, Universidade do Algarve, 2008

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Without the top-down effects and the external/physical forcing, a stable coexistence of two phytoplankton species under a single resource is impossible — a result well known from the principle of competitive exclusion. Here I demonstrate by analysis of a mathematical model that such a stable coexistence in a homogeneous media without any external factor would be possible, at least theoretically, provided (i) one of the two species is toxin producing thereby has an allelopathic effect on the other, and (ii) the allelopathic effect exceeds a critical level. The threshold level of allelopathy required for the coexistence has been derived analytically in terms of the parameters associated with the resource competition and the nutrient recycling. That the extra mortality of a competitor driven by allelopathy of a toxic species gives a positive feed back to the algal growth process through the recycling is explained. And that this positive feed back plays a pivotal role in reducing competition pressures and helping species succession in the two-species model is demonstrated. Based on these specific coexistence results, I introduce and explain theoretically the allelopathic effect of a toxic species as a ‘pseudo-mixotrophy’—a mechanism of ‘if you cannot beat them or eat them, just kill them by chemical weapons’. The impact of this mechanism of species succession by pseudo-mixotrophy in the form of alleopathy is discussed in the context of current understanding on straight mixotrophy and resource-species relationship among phytoplankton species.

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Detailed studies of anomalous conductors in otherwise homogeneous media have been modelled. Vertical contacts form common geometries in galvanic studies when describing geological formations with different electrical conductivities on either side. However, previous studies of vertical discontinuities have been mainly concerned with isotropic environments. In this paper, we deal with the effect on the electric potentials, such as mise-`a-la-masse anomalies, due to a conductor near a vertical contact between two anisotropic regions. We also demonstrate the interactive effects when the conductive body is placed across the vertical contact. This problem is normally very difficult to solve by the traditional numerical methods. The integral equations for the electric potential in anisotropic half-spaces are established. Green’s function is obtained using the reflection and transmission image method in which five images are needed to fit the boundary conditions on the vertical interface and the air-earth surface. The effects of the anisotropy of the environments and the conductive body on the electric potential are illustrated with the aid of several numerical examples.

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A interpretação de anomalias gravimétricas é de grande importância no estudo de feições geológicas que ocorrem na crosta terrestre. Esta interpretação é, no entanto, dificultada pelo fato das anomalias gravimétricas serem resultantes da soma total dos efeitos produzidos por todos os contrastes de densidades de subsuperfície. Desse modo, com o intuito de separar efeitos de feições mais profundas de efeitos de feições mais rasas, bem como a caracterização da geometria desses dois conjuntos de feições, apresentamos um método de separação das componentes regional e residual do campo e a subsequente interpretação de cada componente. A separação regional-residual de dados gravimétricos é efetuada através da aproximação do campo regional por um polinômio ajustado ao campo observado por um método robusto. Este método é iterativo e usa como aproximação inicial a solução obtida através do ajuste polinomial pelo método dos mínimos quadrados. O método empregado minimiza a influência de observações contendo forte contribuição do campo residual no ajuste do campo regional. A componente regional obtida a partir da separação regional-residual é transformada em um mapa de distâncias verticais em relação a um nível de referência. Esta transformação compreende duas etapas. A primeira consiste na obtenção da continuação para baixo da componente regional, que é pressuposta ser causada por uma interface suave separando dois meios homogêneos, representando a interface crosta-manto, cujo contraste de densidade é supostamente conhecido. A segunda consiste na transformação do mapa de continuação para baixo em um mapa de distâncias verticais entre o nível de continuação (tomado como nível de referência) e a interface. Este método apresenta duas dificuldades. A primeira está ligada à instabilidade, havendo portanto a necessidade do emprego de um estabilizador o que acarreta a perda de resolução das feições que se desejam mapear. A segunda, inerente ao método gravimétrico, consiste na impossibilidade da determinação das profundidades absolutas da interface em cada ponto, bastando entretanto o conhecimento da profundidade absoluta em um ponto, através de informação independente, para que todas as outras profundidades absolutas sejam conhecidas. A componente residual obtida a partir da separação regional-residual é transformada em um mapa de contrastes de densidade aparente. Esta transformação consiste no cálculo do contraste de densidade de várias fontes prismáticas através de uma inversão linear pressupondo que as fontes reais estejam das a uma placa horizontal, com contrastes de densidade variando apenas nas direções horizontais. O desempenho do método de separação regional-residual apresentado foi avaliado, através de testes empregando dados sintéticos, fornecendo resultados superiores em relação aos métodos dos mínimos quadrados e da análise espectral. O método de interpretação da componente regional teve seu desempenho avaliado em testes com dados sintéticos onde foram produzidos mapeamentos de interfaces bem próximas das estruturas reais. O limite de resolução das feições que se desejam mapear depende não só do grau do polinômio ajustante, como também da própria limitação inerente ao método gravimétrico. Na interpretação da componente residual é necessário que se postule ou tenha informação a priori sobre a profundidade do topo e espessura da placa onde as fontes estão supostamente confinadas. No entanto, a aplicação do método em dados sintéticos, produziu estimativas razoáveis para os limites laterais das fontes, mesmo na presença de fontes interferentes, e pressupondo-se valores para profundidade do topo e espessura da placa, diferentes dos valores verdadeiros. A ambiguidade envolvendo profundidade do topo, espessura e densidade pode ser visualizada através de gráficos de valores de densidade aparente contra profundidade do topo presumida para a placa para vários valores postulados para a espessura da placa. Estes mesmos gráficos permitem, pelo aspecto das curvas, a elaboração de uma interpretação semi-quantitativa das profundidades das fontes reais. A seqüência dos três métodos desenvolvidos neste trabalho foi aplicada a dados gravimétricos da região norte do Piauí e noroeste do Ceará levando a um modelo de organização crustal que compreende espessamentos e adelgaçamentos crustais associados a um evento compressivo que possibilitou a colocação de rochas densas da base da crosta a profundidades rasas. Este modelo ê compatível com os dados geológicos de superfície. É ainda sugerida a continuidade, por mais 200 km em direção a sudoeste, do Cinturão de Cisalhamento Noroeste do Ceará por sob os sedimentos da Bacia do Parnaíba, com base nas evidências fornecidas pela interpretação da anomalia residual. Embora esta seqüência de métodos tenha sido desenvolvida com vistas ao estudo de feições crustais de porte continental, ela também pode ser aplicada ao estudo de feições mais localizadas como por exemplo no mapeamento do relevo do embasamento de/bacias sedimentares onde os sedimentos são cortados por rochas intrusivas mais densas.

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O problema do mapeamento de uma interface separando dois meios homogêneos tem sido tradicionalmente resolvido através da continuação para baixo da anomalia gravimétrica observada. Este procedimento requer a utilização de um filtro passa-baixa ou de um parâmetro de amortecimento, que tendem a diminuir a resolução do relevo estimado da interface. Além disso, o uso da continuação para baixo implica supor (desnecessariamente) que a interface é uma superfície harmônica. Desta forma, a utilização da continuação para baixo é restrita a interfaces que apresentam um relevo suave relativamente à sua profundidade média. As restrições impostas pela continuação para baixo do campo gravimétrico são reduzidas na técnica de inversão proposta para este estudo, cujo objetivo é mapear a interface crosta-manto baseada na incorporação de informações a priori sobre o mínimo momento de inércia da fonte causadora, em relação a um eixo de concentração de massa pré-estabelecido e coincidente com o topo da fonte anômala. Além da introdução de informações sobre o mínimo momento, foi incluída também a possibilidade de haver variação lateral e em profundidade de densidade em setores previamente estabelecidos, o que permite estender a aplicação desta técnica a situações geológicas mais complexas que envolvam a reconstituição de corpos justapostos, que sejam de diferentes naturezas, tais como aqueles presentes em zonas de transição crustal. O método de inversão apresentado foi avaliado em testes usando dados sintéticos e os resultados obtidos mostraram a eficiência desta técnica em recuperar corpos alongados horizontalmente, que apresentem como topo ou base, interfaces arbitrárias a serem mapeadas. Foi também constatada a eficácia do método em reconstituir corpos que comportem variação lateral de densidade que pudessem retratar situações em que se deseja investigar a natureza do embasamento em regiões de transição crustal. Com base nos resultados destes testes, a técnica foi então empregada na inversão gravimétrica de cinco perfis do LEPLAC IV que cruzam a região oceânica adjacente à margem continental sudeste brasileira. Os resultados desta aplicação permitiram inferir a natureza dos corpos que constituem o arcabouço estrutural da região onde encontram-se inseridas a Dorsal de São Paulo e a Zona de Fratura de Porto Alegre, assim como mapear a Moho subjacente.

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This work describes the covalent immobilization of an ironporphyrin, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron(III) chloride (FeTFPP), onto maghemite/silica magnetic nanospheres covered with aminofunctionalized silica. The resulting material (gamma-Fe2O3/SiO2-NHFeP) was characterized by diffuse reflectance infrared spectroscopy (DRIFTS) and UV-Vis absorption spectroscopy. The catalytic activity of this magnetic ironporphyrin was investigated in the oxidation of hydrocarbons (styrene, (Z)-cyclooctene and R-(+)-limonene) and an herbicide (simazine) by hydrogen peroxide or 3-chloroperoxybenzoic acid. Hydrocarbon and simazine oxidation reaction products were analyzed by gas chromatography (GC) and high performance liquid chromatography (HPLC), respectively. This catalytic system proved to be efficient and selective for hydrocarbon oxidation, leading to high product yields from styrene (89%), cyclooctene (71%) and R-(+) -limonene (86%). Simazine oxidation was attained with 100% selectivity for a dechlorinated product (OEAT), while several oxidation products were obtained for the same catalyst in homogeneous media. The catalyst can be easily recovered through application of an external magnetic field and washed after reaction. Catalyst reuse experiments for R-(+)-limonene oxidation have shown that the catalytic activity is kept at 90% after 10 consecutive reactions.

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This work describes the covalent immobilization of an ironporphyrin, 5,10,15,20- tetrakis(pentafluorophenyl)porphyrin iron(III) chloride (FeTFPP), onto maghemite/silica magnetic nanospheres covered with aminofunctionalized silica. The resulting material (γ-Fe2O3/SiO2-NHFeP) was characterized by diffuse reflectance infrared spectroscopy (DRIFTS) and UV-Vis absorption spectroscopy. The catalytic activity of this magnetic ironporphyrin was investigated in the oxidation of hydrocarbons (styrene, (Z)-cyclooctene and R-(+)-limonene) and an herbicide (simazine) by hydrogen peroxide or 3-chloroperoxybenzoic acid. Hydrocarbon and simazine oxidation reaction products were analyzed by gas chromatography (GC) and high performance liquid chromatography (HPLC), respectively. This catalytic system proved to be efficient and selective for hydrocarbon oxidation, leading to high product yields from styrene (89%), cyclooctene (71%) and R-(+)-limonene (86%). Simazine oxidation was attained with 100% selectivity for a dechlorinated product (OEAT), while several oxidation products were obtained for the same catalyst in homogeneous media. The catalyst can be easily recovered through application of an external magnetic field and washed after reaction. Catalyst reuse experiments for R-(+)-limonene oxidation have shown that the catalytic activity is kept at 90% after 10 consecutive reactions.